US20200010640A1 - Use of at least one phenolic compound to stabilise ethylene copolymerisation reactions - Google Patents
Use of at least one phenolic compound to stabilise ethylene copolymerisation reactions Download PDFInfo
- Publication number
- US20200010640A1 US20200010640A1 US16/468,033 US201716468033A US2020010640A1 US 20200010640 A1 US20200010640 A1 US 20200010640A1 US 201716468033 A US201716468033 A US 201716468033A US 2020010640 A1 US2020010640 A1 US 2020010640A1
- Authority
- US
- United States
- Prior art keywords
- radical
- phenolic compound
- ethylene
- formula
- branched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002989 phenols Chemical class 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 65
- 239000005977 Ethylene Substances 0.000 title claims description 64
- 239000003999 initiator Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 41
- -1 C1-C8 alkyl radical Chemical class 0.000 claims description 39
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 38
- 150000003254 radicals Chemical class 0.000 claims description 32
- 150000001451 organic peroxides Chemical class 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 229930003427 Vitamin E Natural products 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 19
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 19
- 235000019165 vitamin E Nutrition 0.000 claims description 19
- 229940046009 vitamin E Drugs 0.000 claims description 19
- 239000011709 vitamin E Substances 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 claims description 7
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 claims description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 16
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 0 [1*]C1=C(O)C([2*])=C([3*])C([4*])=C1[5*] Chemical compound [1*]C1=C(O)C([2*])=C([3*])C([4*])=C1[5*] 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 244000045947 parasite Species 0.000 description 5
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 230000003019 stabilising effect Effects 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BRQMAAFGEXNUOL-LLVKDONJSA-N [(2R)-2-ethylhexyl] (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCC[C@@H](CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-LLVKDONJSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IJRVDOPVQJSPRP-UHFFFAOYSA-N octan-4-yl prop-2-enoate Chemical compound CCCCC(CCC)OC(=O)C=C IJRVDOPVQJSPRP-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
Definitions
- the present invention relates to the use of one or more phenolic compounds, as defined below, to stabilise ethylene copolymer reactions at high pressure.
- the invention also relates to a method of preparing an ethylene copolymer at high pressure in the presence of one or more phenolic compounds, as defined below, and one or more initiators.
- Low-density polyethylenes also known as LDPE
- ethylene copolymers are usually prepared in an autoclave or tubular reactor under very high pressure, by continuous introduction of ethylene, of one or more optional comonomers and of one or more initiators, such as organic peroxides, typically diluted in an organic solvent.
- the pressure inside the reactor is typically comprised from 500 to 5000 bar while the temperature, during reaction initiation, most often varies from 80 to 250° C.
- the maximum reaction temperature is typically comprised from 120 to 350° C.
- the degree of conversion into polymer generally obtained with this type of method is on the order of from 15% to 25%.
- productivity of a method expressed in grams of polyethylene or ethylene copolymer produced per gram of peroxide initiator used, may vary from 1000 to 3000 g/g, and is often less than 2500 g/g.
- Producers of polyethylene and ethylene copolymer are constantly seeking to obtain production gains and thus streamline costs. In particular, it is important to seek to implement a method enabling the manufacture of polyethylene or ethylene copolymers at a high rate of productivity while maintaining good reliability.
- ethylene copolymers can be used to manufacture cables, thermomelt adhesive compositions, multi-layer wrapping films, or masterbatches. They can also be used as impact modifiers in the preparation of polymers such as polyamides and polyesters for the electronics and automotive sectors.
- one of the purposes of the present invention is to reduce the frequency of the ethylene decomposition during ethylene copolymerisation processes at high pressure in order to improve their productivity and reduce the maintenance costs associated with this decomposition.
- this document discloses that a mixture consisting of ethylene and one or more optional comonomers is heated to a temperature that is sufficient to allow organic peroxides, when introduced into the mixture, to decompose into free radicals in order to more effectively trigger polymerisation.
- the monomer mixture is preheated prior to the introduction of the organic peroxides, at the start of the reactor in equipment provided for this purpose.
- this reaction mixture tends to polymerise easily on the preheater walls.
- This unwanted polymerisation results in limiting the heat transfer to the organic peroxides, which prevents them from forming free radicals and enabling polymerisation to start under optimal operating conditions.
- This parasite reaction fouls the walls of the device used for preheating.
- the hindered phenolic compounds are thus added to the monomer mixture prior to the introduction of organic peroxides in order to reduce or eliminate parasite polymerisation occurring during the preheating stage and therefore reduce fouling at the beginning of the reactor.
- the phenolic compounds are used to reduce the parasite polymerisation that occurs in the monomer mixture before the radical polymerisation initiated by organic peroxides begins in the reaction area.
- one particular subject-matter of the invention is the use of at least one phenolic compound of the following Formula (I):
- the phenolic compound(s) of Formula (I) present the advantage to significantly decrease the frequency of the ethylene decomposition in a reaction mixture comprising other monomers during the radical copolymerisation of the ethylene at high pressure in the presence of initiators.
- the phenolic compound(s) according to the invention permit(s) to decrease the sensitivity of the ethylene to the concentration of the initiators (such as organic peroxides, oxygen) thereby limiting their degradation into carbon, methane, and hydrogen.
- the initiators such as organic peroxides, oxygen
- the phenolic compound(s) according to the invention permit(s) to improve the productivity of the ethylene copolymer preparation methods while minimising maintenance costs.
- the phenolic compound(s) according to the invention has (have) the advantage of significantly reducing the frequency of the ethylene decomposition compared to the use of butyl hydroxytoluene under the same conditions.
- the invention also relates to a method for preparing ethylene copolymers comprising a radical ethylene copolymerisation step at high pressure in the presence of one or more initiators and one or more phenolic compounds as defined above.
- the method of preparation according to the invention offers a high level of productivity and reliability.
- the present invention also relates to a polymer composition obtained by radical copolymerisation of the ethylene at high pressure in the presence of one or more initiators and one or more phenolic compounds of Formula (I).
- high pressure means a pressure greater than 50 MPa.
- the pressure varies from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), and more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- a “phenolic compound” is a compound comprising at least one phenol in its structure.
- the phenolic compound(s) used to stabilise the reactions during the radical copolymerisation of the ethylene at high pressure are of Formula (I) as previously described.
- R 1 does not represent a branched C- 1 -C 8 alkyl radical.
- R 4 and R 5 can together form a five- or six-member cycle comprising an oxygen atom; said cycle being substituted by a C 1 -C 17 alkyl radical, linear or branched.
- the phenol cycle can be condensed on a five- or six-member cycle comprising an oxygen atom; said cycle being substituted by a C- 1 -C 17 alkyl radical, linear or branched, preferably branched.
- the phenolic compound(s) correspond to the following Formula (I):
- R 1 , R 2 and R 3 can preferably represent a linear C- 1 -C 4 , alkyl radical, in particular a methyl radical.
- R 1 and R 3 can preferably represent a linear C 1 -C 4 alkyl radical, in particular a methyl radical, and R 2 represents a hydrogen atom.
- R 2 and R 3 can preferably represent a linear C 1 -C 4 alkyl radical, in particular a methyl radical, and Rirepresents a hydrogen atom.
- R 1 and R 2 can preferably represent a hydrogen atom and R 3 represents a linear C 1 -C 4 alkyl radical, in particular a methyl radical.
- phenolic compound(s) is or are preferentially chosen from the following Formula (I′):
- the phenolic compound of Formula (I) is chosen from 2,5-di-tert-butylhydroquinone, 2,5-di(tert-amyl)hydroquinone, vitamin E and monomethyl ether hydroquinone (MEHQ) and mixtures thereof.
- the phenolic compound(s) according to the invention is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- the phenolic compound according to the invention is vitamin E.
- the phenolic compound according to the invention corresponds to Formula (I′).
- the phenolic compound(s) of Formula (I) is or are used to stabilise the radical ethylene copolymerisation reactions at high pressure in the presence of one or more initiators.
- the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions at high pressure initiated by one or more initiators.
- the phenolic compound(s) of Formula (I) is or are used in a reaction mixture comprising at least ethylene and one or more initiators to stabilise the radical ethylene copolymerisation reactions at high pressure.
- stabilise the radical ethylene copolymerisation reactions means reducing the reactions of the decompostion (or degradation) of the ethylene into carbon, hydrogen and methane that occur during the radical copolymerisation reaction of the ethylene and are caused by excess initiators (organic peroxides and/or oxygen).
- the phenolic compound(s) of Formula (I) is or are used to limit the decomposition of the ethylene during radical ethylene copolymerisation reactions at high pressure.
- the phenolic compound(s) is or are used to limit the number and speed of the reactions of the ethylene decomposition into carbon, hydrogen and methane during radical ethylene copolymerisation reactions at high pressure that are initiated by one or more initiators.
- the initiator(s) enable(s) free radicals to be formed in order to initiate the radical copolymerisation of the ethylene.
- the initiator(s) can trigger the radical copolymerisation of the ethylene.
- the initiator(s) can be chosen from the organic peroxides, oxygen, azobisisobutyronitrile (AIBN) and mixtures thereof.
- the initiator(s) is or are chosen from the organic peroxides, oxygen and mixtures thereof.
- the initiator(s) is or are chosen from the organic peroxides.
- the organic peroxides are chosen from the peroxy esters, dialkyl peroxides, hydroperoxides or peroxyketals.
- Such peroxides are in particular marketed by Arkema under the brand name Luperox®.
- peroxy esters can include t-butyl peroxy-2-ethylhexanoate (Luperox 26), t-butyl peroxyacetate (Luperox 7), t-amyl peroxyacetate (Luperox 555), t-butyl perbenzoate (Luperox P), t-amyl perbenzoate (Luperox TAP) and OO-t-butyl 1-(2-ethylhexyl)monoperoxycarbonate (Luperox TBEC).
- dialkyl peroxides can include 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane (Luperox 101), dicumyl peroxide (Luperox DC), 1′alpha-alpha'-bis (t-butylperoxy) diisopropylbenzene (Luperox F40), di-t-butyl-peroxide (Luperox DI), di-t-amyl-peroxide (Luperox DTA) and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3 (Luperox 130).
- dialkyl peroxides can include 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane (Luperox 101), dicumyl peroxide (Luperox DC), 1′alpha-alpha'-bis (t-butylperoxy) diisopropylbenzene (Lup
- tert-butyl-hydroperoxide (Luperox TBH 70) can be mentioned.
- peroxyketals can include 1,1-di-(t-butylperoxy)-3,3,5- trimethylcyclohexane (Luperox 231), ethyl-3,3-di-(t-butylperoxybutyrate) (Luperox 233) or ethyl-3,3-di-(t-amylperoxybutyrate) (Luperox 533).
- the organic peroxides are chosen from the dialkyl peroxides, particularly 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane sold under the brand name Luperox 101.
- the organic peroxide(s) is or are generally diluted in a solvent or a mixture of solvents.
- the solvent(s) can be chosen from the C 1 -C 20 alkanes, particularly C 3 -C 10 , and more particularly C 5 -C 8 , and preferentially heptane.
- the phenolic component(s) of Formula (I) are used in particular to stabilise the radical ethylene copolymerisation reactions with other comonomers.
- said comonomers are chosen from the unsaturated carboxylic acids (or their salts), the anhydrides of carboxylic acids, the vinyl esters such as vinyl acetate or pivalate acetate, the alpha-olefins such as propene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, the unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid and fumaric acid, the (meth)acrylic acid derivatives such as (meth)acrylonitrile and (meth)acrylic amide, the vinyl esters such as vinyl methyl ether and vinyl phenyl ether and the aromatic vinyl compounds such as styrene and alpha-methyl styrene, or carbon monoxide, or mixtures thereof.
- the unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid and fumaric acid, the (meth)acrylic acid derivatives such as (meth)acrylonitrile and (
- the comonomer(s) are chosen from esters of unsaturated carboxylic acids (or their salts), carboxylic acid anhydrides, and mixtures thereof.
- esters of unsaturated carboxylic acid are preferably chosen from the (meth)alkyl acrylates, particularly the C 1 -C 24 (meth)alkyl acrylates, and the (meth)acrylates comprising an epoxy group.
- the alkyl (meth)acrylates are chosen from among methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
- the (meth)acrylates comprising an epoxy group are chosen from among glycidyl methacrylate, glycidyl acrylate.
- the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions with comonomers chosen from a mixture of unsaturated carboxylic acid esters and the anhydrides of carboxylic acid in the presence of one or more initiators.
- the phenolic compound(s) of Formula (I) is or are used to stabilise the ethylene copolymerisation reactions with a mixture of comonomers comprising methyl acrylate and glycidyl methacrylate.
- the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions between the ethylene and a mixture of comonomers comprising methyl acrylate and glycidyl methacrylate in the presence of one or more initiators chosen from the organic peroxides, oxygen, or mixtures thereof.
- the invention also relates to a method for preparing ethylene copolymers that includes a radical ethylene copolymerisation step at high pressure in the presence of one or more initiators as described above, and one or more phenolic compounds as described above.
- the initiator(s) is or are chosen from the organic peroxides, oxygen, and mixtures thereof.
- the phenolic compound(s) according to the invention is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- MEHQ monomethyl ether hydroquinone
- the phenolic compound according to the invention is vitamin E.
- the phenolic compound corresponds to the previous Formula (I′).
- the phenolic compound(s) is or are preferably present in an amount by weight comprised from 100 to 50,000 ppm relative to the amount by weight of the comonomers.
- the phenolic compound(s) is or are solubilised in an organic solvent, preferably a hydrocarbon-, alcohol-, or ketone-type organic solvent, yet more preferably a hydrocarbon-type organic solvent, in particular isododecane, before being introduced into the reactor, preferably in an amount of from 5 and 80% by weight, relative to the amount by weight of the solvent.
- an organic solvent preferably a hydrocarbon-, alcohol-, or ketone-type organic solvent, yet more preferably a hydrocarbon-type organic solvent, in particular isododecane
- the phenolic compound(s) is or are solubilised in the comonomer(s) before being introduced into the reactor, preferably in an amount by weight of 100 to 50,000 ppm relative to the amount by weight of the comonomer(s).
- the initiator(s) is or are preferably present in an amount by weight of between 20 and 1000 ppm relative to the amount by weight of the ethylene.
- the copolymerisation of the ethylene is done at an initiation temperature of from 100 to 200° C., preferably from 120 to 160° C.
- the copolymerisation takes place at a pressure of from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- the high pressure copolymerisation is generally carried out in an autoclave or tubular reactor.
- the reaction temperature is generally comprised from 150 to 320° C.
- the mixture of ethylene and any comonomer(s) is preferably introduced at the top of the tubular reactor.
- the initiator or mixture of initiators is injected with a high-pressure pump at the top of the reactor, downstream of the inlet for the mixture of ethylene and any comonomer(s).
- the mixture of the ethylene and any optional comonomers can be injected at at least one other point of the reactor; this injection is followed by a repeat injection of initiator or mixture of initiators, known as the multipoint injection technique.
- the mixture is preferably injected such that the weight ratio of the mixture injected on input into the reactor to the total mixture injected is comprised from 10 to 90%.
- tubular high-pressure polymerisation or copolymerisation that can be used are for example those disclosed in US2006/0149004 A1 or in US2007/0032614 A1.
- An autoclave reactor can also be used to carry out the high-pressure radical polymerisation.
- An autoclave reactor generally consists of a cylindrical reactor into which a stirrer is placed. The reactor can be separated into several zones connected to one another in sequence.
- the method according to the invention is implemented in an autoclave reactor.
- the time spent in the reactor is comprised from 30 to 120 seconds.
- the length/diameter ratio of the reactor is comprised from 3 to 25.
- the ethylene and comonomer(s) are injected into the reaction area(s) at a temperature comprised from 50 to 120° C.
- the ethylene and comonomer(s) are injected into the reaction area(s) at a temperature strictly below 100° C., preferably at a temperature strictly below 80° C.
- the method for preparing ethylene copolymers according to the invention does not include a preheating step of the monomers prior to their introduction into the reaction area(s).
- the injection of one or more initiators into the reaction mixture begins at a temperature strictly below 100° C., preferably at a temperature strictly below 80° C.
- the method for preparing ethylene copolymers according to the invention does not include a preheating step of the monomers prior to the introduction of said one or more initiators.
- an initiator is also injected into this first reaction area when the reaction area reaches a temperature comprised from 150 to 200° C.
- the temperature can be comprised from 150 to 320° C. because the reaction is exothermic. If the reactor is a multizone reactor, the feed of ethylene and any optional comonomers which have not reacted as well as the polymer formed then go through the subsequent reaction zones.
- ethylene, comonomers and initiators can be injected at an initiation temperature comprised from 150 to 200° C.
- the temperature of the zones after initiation is comprised from 150 to 320° C.
- the reactor pressure varies from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- Another subject-matter of the present invention relates to the product resulting from the radical ethylene copolymerisation at high pressure in the presence of one or more initiators as described above and of one or more phenolic compounds as described above.
- the product is a polymer composition (or polymer product) that is a result of the radical ethylene copolymerisation at high pressure between the ethylene and other comonomers in the presence of one or more initiators as described above and of one or more phenolic compounds as described above.
- the polymer product or polymer composition thus obtained can be used in any type of application, in particular for packaging, and notably food packaging.
- the initiator(s) is or are chosen from the organic peroxides, oxygen and mixtures thereof.
- the polymer composition comprises the ethylene copolymer and the phenolic compound(s) as described above.
- the phenolic compound(s) is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- MEHQ monomethyl ether hydroquinone
- the polymer composition comprises vitamin E.
- the phenolic compound corresponds to the previous Formula (I′).
- one or more additives can be added to the polymer composition.
- the additive is preferably chosen from the antioxidants, UV protection agents, and processing agents, for the purposes of improving the final appearance when it is used, such as fatty amides, stearic acid and its salts, ethylenebis-stearamide or fluoropolymers; antifogging agents; antiblocking agents such as silica or talc; fillers such as calcium carbonate and nanofillers such as, for example, clays; coupling agents such as silanes; crosslinking agents such as peroxides different to those used as radical copolymerisation initators; antistatic agents; nucleating agents; pigments; dyes; plasticisers; fluidisers and flame-retardant additives such as aluminium hydroxide or magnesium hydroxide.
- antioxidants such as fatty amides, stearic acid and its salts, ethylenebis-stearamide or fluoropolymers
- antifogging agents such as silica or talc
- fillers such as calcium carbonate and nanofillers such as, for
- additives are generally used at contents comprised from 10 ppm to 10,000 ppm by weight relative to the weight of the final polyethylene or ethylene copolymer.
- plasticisers, fluidisers and flame-retardant additives can be present in amounts well above 10,000 ppm.
- This equipment operates continuously at pressures comprised from 500 to 2200 bar.
- the reactor wall temperature is set at 200° C. by means of heater rods placed in the walls of the reactor. Stirring is at 1540 rpm (revolutions per minute).
- the temperature of the reaction medium in the reactor is measured by means of four thermocouples.
- the reaction mixture is comprised of an ethylene mixture and acrylates which continuously flows into the reactor with residence time that can vary from 30 seconds to 120 seconds.
- the stabilising agent phenolic compound
- the stabilising agent is introduced in mixture with acrylates.
- the polymerisation initiator is continuously introduced into the reactor in amounts that enable a temperature of about 210° C. to be reached.
- the polymer/monomer mixture is directly decompressed to three bars and the polymer is separated from the ethylene/acrylates mixture that did not react through a separation pot.
- the peroxide flow is then gradually increased every 4 minutes until decomposition is achieved (sometimes this limit is not reached), which enables the decomposition limits (or peroxide concentration sensitivity) to be determined.
- the efficacy of the stabilising agent is determined by the amount of peroxides injected to achieve decomposition: the higher the amount of peroxide, the more effective the stabilising agent.
- Trial #1 Testing with 230 ppm Moles of Stabilising Agent/Acrylate
- vitamin E was compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates.
- BHT butyl hydroxytoluene
- Vitamin E enables greater stabilisation of the ethylene copolymerisation reactions, as ethylene decomposition is achieved at much higher concentrations of organic peroxides than with butyl hydroxytoluene (BHT).
- Test #2 Testing with 460 ppm Moles of Stabilising Agent/Acrylate
- vitamin E and monomethyl ether hydroquinone (MEHQ) were compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates.
- MEHQ monomethyl ether hydroquinone
- BHT butyl hydroxytoluene
- Vitamin E and monomethyl ether hydroquinone (MEHQ) enable greater stabilisation of the ethylene copolymerisation reactions than with butyl hydroxytoluene (BHT) as ethylene decomposition is achieved at much higher concentrations of organic peroxides.
- vitamin E was compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates.
- BHT butyl hydroxytoluene
- Vitamin E enables greater stabilisation of the ethylene copolymerisation reactions than with butyl hydroxytoluene (BHT) as ethylene decomposition is achieved at much higher concentrations of organic peroxides.
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Abstract
Description
- The present invention relates to the use of one or more phenolic compounds, as defined below, to stabilise ethylene copolymer reactions at high pressure.
- The invention also relates to a method of preparing an ethylene copolymer at high pressure in the presence of one or more phenolic compounds, as defined below, and one or more initiators.
- Low-density polyethylenes (also known as LDPE) and ethylene copolymers are usually prepared in an autoclave or tubular reactor under very high pressure, by continuous introduction of ethylene, of one or more optional comonomers and of one or more initiators, such as organic peroxides, typically diluted in an organic solvent. The pressure inside the reactor is typically comprised from 500 to 5000 bar while the temperature, during reaction initiation, most often varies from 80 to 250° C. The maximum reaction temperature is typically comprised from 120 to 350° C.
- The degree of conversion into polymer generally obtained with this type of method is on the order of from 15% to 25%. Similarly, the productivity of a method, expressed in grams of polyethylene or ethylene copolymer produced per gram of peroxide initiator used, may vary from 1000 to 3000 g/g, and is often less than 2500 g/g.
- Producers of polyethylene and ethylene copolymer are constantly seeking to obtain production gains and thus streamline costs. In particular, it is important to seek to implement a method enabling the manufacture of polyethylene or ethylene copolymers at a high rate of productivity while maintaining good reliability.
- This increased productivity gain is all the more important as polyethylenes and ethylene copolymers are of particular commercial interest because they can be used in various fields of application due to their compatibility with many other polymers or resins.
- For example, ethylene copolymers can be used to manufacture cables, thermomelt adhesive compositions, multi-layer wrapping films, or masterbatches. They can also be used as impact modifiers in the preparation of polymers such as polyamides and polyesters for the electronics and automotive sectors.
- However, producers of polyethylene and ethylene copolymer frequently encounter phenomena such as runaway reactions and thermal decomposition of the ethylene because such reactions are performed at high temperature and high pressure.
- In particular, under these operating conditions, during the polymerisation reaction in the presence of excess initiators (organic peroxides, oxygen), ethylene decomposes explosively by leading to the formation of carbon, methane and hydrogen.
- These parasite reactions in the degradation of the ethylene due to excessive initiators, under the aforementioned operating conditions, lead at best to the production of coloured granules (soft decomposition), and at the worst to a rapid rise in pressure and temperature (violent decomposition) in the reactor that triggers production stoppage and costly maintenance operations.
- Thus, one of the purposes of the present invention is to reduce the frequency of the ethylene decomposition during ethylene copolymerisation processes at high pressure in order to improve their productivity and reduce the maintenance costs associated with this decomposition.
- In other words, there is a real need to implement a method for copolymerising ethylene wherein the ethylene copolymer reactions at high pressure are stabilised by minimising the risk of ethylene degradation.
- The document WO 2013/149698 describes the use of hindered phenolic compounds to reduce fouling in the polyethylene polymerisation reactors.
- In particular, this document discloses that a mixture consisting of ethylene and one or more optional comonomers is heated to a temperature that is sufficient to allow organic peroxides, when introduced into the mixture, to decompose into free radicals in order to more effectively trigger polymerisation. Thus, the monomer mixture is preheated prior to the introduction of the organic peroxides, at the start of the reactor in equipment provided for this purpose.
- However, during this preheating step, this reaction mixture tends to polymerise easily on the preheater walls.
- This unwanted polymerisation results in limiting the heat transfer to the organic peroxides, which prevents them from forming free radicals and enabling polymerisation to start under optimal operating conditions. This parasite reaction fouls the walls of the device used for preheating.
- The hindered phenolic compounds are thus added to the monomer mixture prior to the introduction of organic peroxides in order to reduce or eliminate parasite polymerisation occurring during the preheating stage and therefore reduce fouling at the beginning of the reactor. In other words, the phenolic compounds are used to reduce the parasite polymerisation that occurs in the monomer mixture before the radical polymerisation initiated by organic peroxides begins in the reaction area.
- This document therefore does not describe the use of phenolic compounds to decrease the frequency of ethylene decomposition during high pressure polymerisation, i.e. in the presence of organic peroxides acting as polymerisation initiators.
- Therefore, one particular subject-matter of the invention is the use of at least one phenolic compound of the following Formula (I):
- Formula (I), wherein:
-
- R1 represents:
- a hydrogen atom;
- a linear C1-C8 alkyl radical;
- a linear C1-C8 hydroxyalkyl radical;
- a hydroxy group;
- R2, R3, R4 and R5, identical or different, represent:
- a hydrogen atom;
- a C1-C8 alkyl radical, linear or branched, optionally substituted by one or more hydroxy radicals;
- a C1-C8 alkoxy radical, linear or branched, optionally substituted by one or more hydroxy radicals;
- a hydroxy group,
- it being understood that R4 and R5 can together form a five- or six-member cycle comprising an oxygen atom; said cycle being substituted by a C1-C17 alkyl radical, linear or branched,
- in order to stabilise the radical ethylene copolymerisation reactions at high pressure in the presence of one or more initiators.
- The phenolic compound(s) of Formula (I) present the advantage to significantly decrease the frequency of the ethylene decomposition in a reaction mixture comprising other monomers during the radical copolymerisation of the ethylene at high pressure in the presence of initiators.
- In other words, the phenolic compound(s) according to the invention permit(s) to decrease the sensitivity of the ethylene to the concentration of the initiators (such as organic peroxides, oxygen) thereby limiting their degradation into carbon, methane, and hydrogen.
- More generally, the phenolic compound(s) according to the invention permit(s) to improve the productivity of the ethylene copolymer preparation methods while minimising maintenance costs.
- In particular, the phenolic compound(s) according to the invention has (have) the advantage of significantly reducing the frequency of the ethylene decomposition compared to the use of butyl hydroxytoluene under the same conditions.
- The invention also relates to a method for preparing ethylene copolymers comprising a radical ethylene copolymerisation step at high pressure in the presence of one or more initiators and one or more phenolic compounds as defined above.
- The method of preparation according to the invention offers a high level of productivity and reliability.
- Indeed, the parasite ethylene degradation reactions, which hinder productivity in a conventional preparation method, are reduced.
- The present invention also relates to a polymer composition obtained by radical copolymerisation of the ethylene at high pressure in the presence of one or more initiators and one or more phenolic compounds of Formula (I).
- Within the meaning of the present invention, “high pressure” means a pressure greater than 50 MPa. Preferably, the pressure varies from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), and more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- Other characteristics and advantages of the invention will be seen more clearly in the following description and examples.
- In the following, and unless otherwise indicated, the ranges of values used in this document are inclusive.
- The expression “at least one” is equivalent to the expression “one or more”.
- Phenolic Compound
- Within the meaning of the invention, a “phenolic compound” is a compound comprising at least one phenol in its structure.
- The phenolic compound(s) used to stabilise the reactions during the radical copolymerisation of the ethylene at high pressure are of Formula (I) as previously described.
- According to Formula (I), R1 does not represent a branched C-1-C8 alkyl radical.
- According to Formula (I), R4 and R5 can together form a five- or six-member cycle comprising an oxygen atom; said cycle being substituted by a C1-C17 alkyl radical, linear or branched.
- Thus the phenol cycle can be condensed on a five- or six-member cycle comprising an oxygen atom; said cycle being substituted by a C-1-C17 alkyl radical, linear or branched, preferably branched.
- Preferably, the phenolic compound(s) correspond to the following Formula (I):
- Formula (I), wherein:
-
- R1 represents:
- a hydrogen atom;
- a linear C-1-C4 radical alkyl;
- R2, R3 and R4, identical or different, represent:
- a hydrogen atom;
- a C1-C5 radical alkyl, linear or branched;
- a hydroxy group;
- R5 represents:
- a hydrogen atom;
- a C1-C5 radical alkyl, linear or branched;
- a C1-C5 radical alkoxy, linear or branched;
- a hydroxy group;
- it being understood that R4 and R5 can together form a six-member cycle comprising an oxygen atom; said cycle being substituted by a branched C1-C17 alkyl radical.
- Preferably, in Formula (I):
-
- R1, R2 and R3, identical or different, represent:
- a hydrogen atom;
- a linear C1-C4 alkyl radical; and
- R4 and R5 together form a six-member cycle comprising an oxygen atom; said cycle being substituted by a branched C1-C17 alkyl radical.
- More preferably, in Formula (I):
-
- R1, R2 and R3, identical or different, represent:
- a hydrogen atom;
- a methyl radical; and
- R4 and R5together form a six-member cycle comprising an oxygen atom; said cycle being substituted by a branched C1-C17 alkyl radical.
- According to these embodiments, R1, R2 and R3 can preferably represent a linear C-1-C4, alkyl radical, in particular a methyl radical.
- According to these embodiments, R1 and R3 can preferably represent a linear C1-C4 alkyl radical, in particular a methyl radical, and R2 represents a hydrogen atom.
- According to these embodiments, R2 and R3 can preferably represent a linear C1-C4 alkyl radical, in particular a methyl radical, and Rirepresents a hydrogen atom.
- According to these embodiments, R1 and R2 can preferably represent a hydrogen atom and R3 represents a linear C1-C4 alkyl radical, in particular a methyl radical.
- In other words, the phenolic compound(s) is or are preferentially chosen from the following Formula (I′):
- Formula (I′) wherein R1, R2 and R3 correspond to the previously-described meanings, in particular those mentioned above in the preferred embodiments.
- Preferably, as an alternative, in Formula (I):
-
- R1, R2, R3 and R5 represent a hydrogen atom; and
- R4 represents a C1-05 alkoxy radical, preferably a methoxy radical.
- Also preferably, as a variant, in Formula (I):
-
- R1 and R3 represent a hydrogen atom;
- R2 and R5 represent a branched C1-C8 alkyl radical, preferably a branched C1-C5 alkyl radical, in particular C4;
- R4 represents a hydroxy group.
- Preferably, the phenolic compound of Formula (I) is chosen from 2,5-di-tert-butylhydroquinone, 2,5-di(tert-amyl)hydroquinone, vitamin E and monomethyl ether hydroquinone (MEHQ) and mixtures thereof.
- More preferably, the phenolic compound(s) according to the invention is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- Even more preferably, the phenolic compound according to the invention is vitamin E.
- In other words, the phenolic compound according to the invention corresponds to Formula (I′).
- Use
- The phenolic compound(s) of Formula (I) is or are used to stabilise the radical ethylene copolymerisation reactions at high pressure in the presence of one or more initiators.
- In other words, the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions at high pressure initiated by one or more initiators.
- In still other terms, the phenolic compound(s) of Formula (I) is or are used in a reaction mixture comprising at least ethylene and one or more initiators to stabilise the radical ethylene copolymerisation reactions at high pressure.
- Within the meaning of this invention, “stabilise the radical ethylene copolymerisation reactions” means reducing the reactions of the decompostion (or degradation) of the ethylene into carbon, hydrogen and methane that occur during the radical copolymerisation reaction of the ethylene and are caused by excess initiators (organic peroxides and/or oxygen).
- In other words, the phenolic compound(s) of Formula (I) is or are used to limit the decomposition of the ethylene during radical ethylene copolymerisation reactions at high pressure.
- More specifically, the phenolic compound(s) is or are used to limit the number and speed of the reactions of the ethylene decomposition into carbon, hydrogen and methane during radical ethylene copolymerisation reactions at high pressure that are initiated by one or more initiators.
- The initiator(s) enable(s) free radicals to be formed in order to initiate the radical copolymerisation of the ethylene.
- In other words, the initiator(s) can trigger the radical copolymerisation of the ethylene.
- The initiator(s) can be chosen from the organic peroxides, oxygen, azobisisobutyronitrile (AIBN) and mixtures thereof.
- Preferably, the initiator(s) is or are chosen from the organic peroxides, oxygen and mixtures thereof.
- Yet more preferably, the initiator(s) is or are chosen from the organic peroxides.
- Preferably, the organic peroxides are chosen from the peroxy esters, dialkyl peroxides, hydroperoxides or peroxyketals.
- Such peroxides are in particular marketed by Arkema under the brand name Luperox®.
- Examples of peroxy esters can include t-butyl peroxy-2-ethylhexanoate (Luperox 26), t-butyl peroxyacetate (Luperox 7), t-amyl peroxyacetate (Luperox 555), t-butyl perbenzoate (Luperox P), t-amyl perbenzoate (Luperox TAP) and OO-t-butyl 1-(2-ethylhexyl)monoperoxycarbonate (Luperox TBEC).
- Examples of dialkyl peroxides can include 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane (Luperox 101), dicumyl peroxide (Luperox DC), 1′alpha-alpha'-bis (t-butylperoxy) diisopropylbenzene (Luperox F40), di-t-butyl-peroxide (Luperox DI), di-t-amyl-peroxide (Luperox DTA) and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3 (Luperox 130).
- For hydroperoxide, tert-butyl-hydroperoxide (Luperox TBH 70) can be mentioned.
- Examples of peroxyketals can include 1,1-di-(t-butylperoxy)-3,3,5- trimethylcyclohexane (Luperox 231), ethyl-3,3-di-(t-butylperoxybutyrate) (Luperox 233) or ethyl-3,3-di-(t-amylperoxybutyrate) (Luperox 533).
- Preferentially, the organic peroxides are chosen from the dialkyl peroxides, particularly 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane sold under the brand name Luperox 101.
- The organic peroxide(s) is or are generally diluted in a solvent or a mixture of solvents. The solvent(s) can be chosen from the C1-C20 alkanes, particularly C3-C10, and more particularly C5-C8, and preferentially heptane.
- The phenolic component(s) of Formula (I) are used in particular to stabilise the radical ethylene copolymerisation reactions with other comonomers.
- Preferably, said comonomers are chosen from the unsaturated carboxylic acids (or their salts), the anhydrides of carboxylic acids, the vinyl esters such as vinyl acetate or pivalate acetate, the alpha-olefins such as propene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, the unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid and fumaric acid, the (meth)acrylic acid derivatives such as (meth)acrylonitrile and (meth)acrylic amide, the vinyl esters such as vinyl methyl ether and vinyl phenyl ether and the aromatic vinyl compounds such as styrene and alpha-methyl styrene, or carbon monoxide, or mixtures thereof.
- More preferably, the comonomer(s) are chosen from esters of unsaturated carboxylic acids (or their salts), carboxylic acid anhydrides, and mixtures thereof.
- The esters of unsaturated carboxylic acid are preferably chosen from the (meth)alkyl acrylates, particularly the C1-C24 (meth)alkyl acrylates, and the (meth)acrylates comprising an epoxy group.
- Preferably, the alkyl (meth)acrylates are chosen from among methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
- Preferably, the (meth)acrylates comprising an epoxy group are chosen from among glycidyl methacrylate, glycidyl acrylate.
- Preferably, the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions with comonomers chosen from a mixture of unsaturated carboxylic acid esters and the anhydrides of carboxylic acid in the presence of one or more initiators.
- Even more preferably, the phenolic compound(s) of Formula (I) is or are used to stabilise the ethylene copolymerisation reactions with a mixture of comonomers comprising methyl acrylate and glycidyl methacrylate.
- Even more preferably, the phenolic compound(s) of Formula (I) are used to stabilise the radical ethylene copolymerisation reactions between the ethylene and a mixture of comonomers comprising methyl acrylate and glycidyl methacrylate in the presence of one or more initiators chosen from the organic peroxides, oxygen, or mixtures thereof.
- Method
- As previously explained, the invention also relates to a method for preparing ethylene copolymers that includes a radical ethylene copolymerisation step at high pressure in the presence of one or more initiators as described above, and one or more phenolic compounds as described above.
- Preferably, the initiator(s) is or are chosen from the organic peroxides, oxygen, and mixtures thereof.
- Preferably, the phenolic compound(s) according to the invention is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- Even more preferably, the phenolic compound according to the invention is vitamin E. In other words, the phenolic compound corresponds to the previous Formula (I′).
- The phenolic compound(s) is or are preferably present in an amount by weight comprised from 100 to 50,000 ppm relative to the amount by weight of the comonomers.
- Preferably, the phenolic compound(s) is or are solubilised in an organic solvent, preferably a hydrocarbon-, alcohol-, or ketone-type organic solvent, yet more preferably a hydrocarbon-type organic solvent, in particular isododecane, before being introduced into the reactor, preferably in an amount of from 5 and 80% by weight, relative to the amount by weight of the solvent.
- Alternatively, the phenolic compound(s) is or are solubilised in the comonomer(s) before being introduced into the reactor, preferably in an amount by weight of 100 to 50,000 ppm relative to the amount by weight of the comonomer(s).
- The initiator(s) is or are preferably present in an amount by weight of between 20 and 1000 ppm relative to the amount by weight of the ethylene.
- The copolymerisation of the ethylene is done at an initiation temperature of from 100 to 200° C., preferably from 120 to 160° C.
- The copolymerisation takes place at a pressure of from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- The high pressure copolymerisation is generally carried out in an autoclave or tubular reactor. The reaction temperature is generally comprised from 150 to 320° C.
- When a tubular reactor is used, the mixture of ethylene and any comonomer(s) is preferably introduced at the top of the tubular reactor. The initiator or mixture of initiators is injected with a high-pressure pump at the top of the reactor, downstream of the inlet for the mixture of ethylene and any comonomer(s).
- The mixture of the ethylene and any optional comonomers can be injected at at least one other point of the reactor; this injection is followed by a repeat injection of initiator or mixture of initiators, known as the multipoint injection technique. When the multipoint injection technique is used, the mixture is preferably injected such that the weight ratio of the mixture injected on input into the reactor to the total mixture injected is comprised from 10 to 90%.
- Other methods of tubular high-pressure polymerisation or copolymerisation that can be used are for example those disclosed in US2006/0149004 A1 or in US2007/0032614 A1.
- An autoclave reactor can also be used to carry out the high-pressure radical polymerisation. An autoclave reactor generally consists of a cylindrical reactor into which a stirrer is placed. The reactor can be separated into several zones connected to one another in sequence.
- Preferably, the method according to the invention is implemented in an autoclave reactor.
- Advantageously, the time spent in the reactor is comprised from 30 to 120 seconds.
- Preferentially, the length/diameter ratio of the reactor is comprised from 3 to 25. The ethylene and comonomer(s) are injected into the reaction area(s) at a temperature comprised from 50 to 120° C.
- Preferably, the ethylene and comonomer(s) are injected into the reaction area(s) at a temperature strictly below 100° C., preferably at a temperature strictly below 80° C.
- Preferably, the method for preparing ethylene copolymers according to the invention does not include a preheating step of the monomers prior to their introduction into the reaction area(s).
- Preferably, the injection of one or more initiators into the reaction mixture begins at a temperature strictly below 100° C., preferably at a temperature strictly below 80° C.
- Preferably, the method for preparing ethylene copolymers according to the invention does not include a preheating step of the monomers prior to the introduction of said one or more initiators.
- Alternatively, an initiator is also injected into this first reaction area when the reaction area reaches a temperature comprised from 150 to 200° C.
- During the reaction the temperature can be comprised from 150 to 320° C. because the reaction is exothermic. If the reactor is a multizone reactor, the feed of ethylene and any optional comonomers which have not reacted as well as the polymer formed then go through the subsequent reaction zones.
- In each reaction area, ethylene, comonomers and initiators can be injected at an initiation temperature comprised from 150 to 200° C. The temperature of the zones after initiation is comprised from 150 to 320° C.
- The reactor pressure varies from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), more preferably from 1200 bar (120 MPa) to 2600 bar (260 MPa).
- Product Resulting from the Polymeriseable Composition
- Another subject-matter of the present invention relates to the product resulting from the radical ethylene copolymerisation at high pressure in the presence of one or more initiators as described above and of one or more phenolic compounds as described above.
- Thus the product is a polymer composition (or polymer product) that is a result of the radical ethylene copolymerisation at high pressure between the ethylene and other comonomers in the presence of one or more initiators as described above and of one or more phenolic compounds as described above.
- The polymer product or polymer composition thus obtained can be used in any type of application, in particular for packaging, and notably food packaging.
- Preferably, the initiator(s) is or are chosen from the organic peroxides, oxygen and mixtures thereof.
- The polymer composition comprises the ethylene copolymer and the phenolic compound(s) as described above.
- Preferably, the phenolic compound(s) is or are chosen from vitamin E and monomethyl ether hydroquinone (MEHQ).
- Even more preferably, the polymer composition comprises vitamin E. In other words, the phenolic compound corresponds to the previous Formula (I′).
- Once the copolymer has been obtained, one or more additives can be added to the polymer composition.
- The additive is preferably chosen from the antioxidants, UV protection agents, and processing agents, for the purposes of improving the final appearance when it is used, such as fatty amides, stearic acid and its salts, ethylenebis-stearamide or fluoropolymers; antifogging agents; antiblocking agents such as silica or talc; fillers such as calcium carbonate and nanofillers such as, for example, clays; coupling agents such as silanes; crosslinking agents such as peroxides different to those used as radical copolymerisation initators; antistatic agents; nucleating agents; pigments; dyes; plasticisers; fluidisers and flame-retardant additives such as aluminium hydroxide or magnesium hydroxide.
- These additives are generally used at contents comprised from 10 ppm to 10,000 ppm by weight relative to the weight of the final polyethylene or ethylene copolymer.
- The plasticisers, fluidisers and flame-retardant additives can be present in amounts well above 10,000 ppm.
- The following examples serve to illustrate the invention, without, however, being limiting in nature.
- The following examples were performed on a 110 ml continuous stirred autoclave micro-pilot.
- This equipment operates continuously at pressures comprised from 500 to 2200 bar. The reactor wall temperature is set at 200° C. by means of heater rods placed in the walls of the reactor. Stirring is at 1540 rpm (revolutions per minute).
- The temperature of the reaction medium in the reactor is measured by means of four thermocouples.
- The reaction mixture is comprised of an ethylene mixture and acrylates which continuously flows into the reactor with residence time that can vary from 30 seconds to 120 seconds. The stabilising agent (phenolic compound) is introduced in mixture with acrylates.
- The polymerisation initiator is continuously introduced into the reactor in amounts that enable a temperature of about 210° C. to be reached. When exiting the reactor, the polymer/monomer mixture is directly decompressed to three bars and the polymer is separated from the ethylene/acrylates mixture that did not react through a separation pot.
- Operating Conditions:
-
- Reactor flow: 4 kg/hr,
- Peroxide used: Diluted Luperox 11 (tert-butyl peroxypivalate) in n-Heptane,
- Residence time in the reactor: approx. 50 seconds,
- Pressure: 1900 bar (190 Mpa),
- Monomers: mixture of acrylates (methyl acrylate and glycidyle methacrylate with mass weights of respectively 5% and 1.5% in feed),
- Stabilising agents: variable amounts that are introduced with acrylic monomers.
- When the reaction has stabilised at the temperature of about 210° C. for approximately 5 to 10 min, the peroxide flow is then gradually increased every 4 minutes until decomposition is achieved (sometimes this limit is not reached), which enables the decomposition limits (or peroxide concentration sensitivity) to be determined.
- The efficacy of the stabilising agent is determined by the amount of peroxides injected to achieve decomposition: the higher the amount of peroxide, the more effective the stabilising agent.
- Trial #1: Testing with 230 ppm Moles of Stabilising Agent/Acrylate
- In this trial, vitamin E was compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates. For each stabilising agent, a minimum of 3 trials was performed. The mean values for the trials are shown in the following table:
-
ppm mole stabilising Mean [C] Peroxide Stabilising agents agent relative to at decomposition (phenolic compounds) acrylates in ppm moles Without stabilising agent — 60.4 BHT 230 108.8 Vitamin E 230 120.0 - The results show that Vitamin E enables greater stabilisation of the ethylene copolymerisation reactions, as ethylene decomposition is achieved at much higher concentrations of organic peroxides than with butyl hydroxytoluene (BHT).
- In these trials, the mean values are significantly different.
- Test #2: Testing with 460 ppm Moles of Stabilising Agent/Acrylate
- In this trial, vitamin E and monomethyl ether hydroquinone (MEHQ) were compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates. For each stabilising agent, a minimum of 3 trials was performed. The mean values for the trials are shown in the following table:
-
ppm mole stabilising Mean [C] Peroxide Stabilising agents agent relative to at decomposition (phenolic compounds) acrylates in ppm moles Without stabilising agent — 60.4 BHT 460 92.9 MEHQ 460 97.3 Vitamin E 460 132.5 - The results show that Vitamin E and monomethyl ether hydroquinone (MEHQ) enable greater stabilisation of the ethylene copolymerisation reactions than with butyl hydroxytoluene (BHT) as ethylene decomposition is achieved at much higher concentrations of organic peroxides.
- Furthermore, the best results were obtained with Vitamin E.
- In these trials, the mean values are significantly different.
- Trials #3: Testing with 115 ppm Moles of Stabilising Agent/Acrylate
- In this trial, vitamin E was compared with butyl hydroxytoluene (BHT) with the same molar concentrations relative to acrylates. For each stabilising agent, a minimum of 3 trials was performed. The mean values for the trials are shown in the following table:
-
ppm mole stabilising Mean [C] Peroxide Stabilising agents agent relative to at decomposition (phenolic compounds) acrylates in ppm moles Without stabilising agent — 60.4 BHT 115 77.2 Vitamin E 115 102.8 - The results show that Vitamin E enables greater stabilisation of the ethylene copolymerisation reactions than with butyl hydroxytoluene (BHT) as ethylene decomposition is achieved at much higher concentrations of organic peroxides.
- In these trials, the mean values are significantly different.
Claims (20)
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US20060141275A1 (en) * | 2004-12-02 | 2006-06-29 | Sumitomo Chemical Company, Limited | Shaped article |
WO2007018871A1 (en) | 2005-08-05 | 2007-02-15 | Exxonmobil Chemical Patents Inc. | Process and apparatus for manufacturing ethylene polymers and copolymers |
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